The forecasted concentration of PM2.5 forecasting model greatly deviate from the measured concentration. In order to solve this problem, the data (from February 2015 to July 2015), consisting of measured PM2.5 concentration, PM2.5 model (WRF-Chem) forecasted concentration and model forecasted data of 5 main meteorological factors, were provided by Shanghai Pudong Meteorological Bureau. Support Vector Machine (SVM) and Particle Swarm Optimization (PSO) algorithm were combined to build rolling forecasting model of hourly PM2.5 concentration in 24 hours in advance. Meanwhile, the nighttime average concentration, daytime average concentration and daily average concentration during the upcoming day were forecasted by rolling model. Compared with Radical Basis Function Neural Network (RBFNN), Multiple Linear Regression (MLR) and WRF-Chem, the experimental results show that the proposed SVM model improves the forecasting accuracy of PM2.5 concentration one hour in advance (according with the results concluded from finished research), and can comparatively well forecast PM2.5 concentration in 24 hours in advance, and effectively forecast the nighttime average concentration, daytime average concentration and daily average concentration during the upcoming day. In addition, the proposed model has comparatively high forecasting accuracies of hourly PM2.5 concentration in 12 hours in advance and nighttime average concentration during the upcoming day.